Use of contact masses



y HouDRY USE OF CONTACT MASSES Find nay 13, 1935 AToRNEY ,who k Feb. 5, 1935.

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Patented F eb. 5, 1935 -PATENT OFFICE USE OF CONTACT MASSES Eugene` J. Houdry, Woodbury, N.y J., assigner to Houdry Process Corporation, Dover, Del., a corporation of Delaware Application May 13, 1933, Serial No. 670,954

1 2 Claims.

This invention relates to chemical reactions involving the use of contact masses', as in the treating and refining of hydrocarbons, especially heavy hydrocarbons such as tarry residues resulting vfrom the conversion and reflningof petroleum and the destructive distillation by pyrobituminous material. More particularly it concerns vaporization of such materials with a view to their subsequent conversion into lighter hydrocarbons. In certain respects it may be considered as a further development of and improvement upon the invention disclosed in United States Patent No. 1,806,997, issued May 26, 1931, to Alfred Joseph.

One object of the invention is to distribute starting material in liquid phase more effectively and uniformly over an absorptive vaporizing mass. Another object is to eiect a heat balance between contact masses involved simultaneously in exothermic and endothermic reactions. Another object is to utilize in a novel manner the combustion of the coke and tarry deposits on a contact mass as the source of most if not all of the heat required for a treating operation. Another .v object is to provide improved apparatus for continuous operation ywith a plurality of vaporizing masses alternately on stream and under purication by combustion. Other objects will be apparent from the detailed description which follows.

In one aspect the invention involves preheating heavystarting material, which may be so viscous as to be non-fluid at atmospheric temperature, as high as possible without cracking. 'I'he preheated oil is then atomized by a hot inert gaseous medium which acts as a vehicle f or the material under -treatment both before and after vaporization. The atomized charge is conducted at high velocity and distributedevenly over anabsorptive contact mass which separates the liquid oil from the gaseous vehicle and holds the cil within its pores at vaporizing temperature until vaporization takes place. The oil vapors then leave the mass to be picked up again by the gaseous vehicle and to be carried away by the latter, while the coke and tarry constituents remain behind in' the pores of lthevaporizing mass. When the coky deposits clog the pores'to such an extent that the vaporizing 'action is impaired, they are removed by a regenerating operation involving oxidation, Awhich may be followed by a solvent treatment, if there has been an `accumulation of other deposits which cannot be burned away. In another aspect the invention involves the use of treating units in adjacent insulated* chambers with ene set of units on stream while the other' set is in regeneration, thus providing for continuous operatiojn, and the heat produced by the oxidation of the deposits in one set of converters may be utilized to provide the heat of vaporization for the other set. Transfer of heat between the chambers may be accomplished by discharging air 'with or without the hot fumes of regeneration from the regenerating chamber into the other chamber. By preference, the heated air is forced in a closed circuit with added heat when neces- 10 sary and with suitable provision for relieving excess of ilue gases. When the functions of the sets of converters change, the 'direction of the circulated heat conducting medium is reversed.

vIn order to illustrate the invention and the 15 manner of its operation, one concrete embodiment thereof is shown in the accompanying' drawing, in which:

Fig. 1 is a plan view, partly in section and largely diagrammatic in character, of one form of y20 apparatus for practising the invention; and

Fig. 2 is a-vertical sectional view substantially on the line 2 2 of Fig. 1.

`The embodiment of the invention shown for the purpose of illustration is intended for con- 25 tinuous operation and comprises an enclosure 3 providing chambers 4 and 5 insulated from one another in which the vaporizing units or converters are mounted. While any numberof such units may be provided of any suitable or desired 30 type, twoy units of an elongate flat type are dis,- closed in each of the insulated chambers, units 6 and 6a in chamber 4 and units 6b and 6c in chamber 5. Details of these units are illustrated in Fig. 2, and will be described later. l

The charging stock, which may be any heavy I hydrocarbon residue, including tars and slop oils, even those which may be non-fluid under atmospheric conditions, is preheated to bring it to fluid condition, if necessary, land then its4 tempera- 40 ture is raised as high as possible without cracking, as to about 600 F. This may be accomplished through heat exchange with hot vapors from any source. In Fig. 1, the charge is illustrated as passing through heat exchanger- 7, 45 where it is in heat exchange relation with the vapors issuing from the converters in enclosure 3. The heated charge then passes by line 8 to branched and valved lines 8a and 8b, which co..- duct it to atomizers 9 and 9a. 'I'he atomizing 50 fluid, which serves as a vehicle for conducting the charge through the apparatus in enclosure 3, may be any hot gaseous material which is inert to the charge under the operating conditions such as nue gas or steam. By preference.

steam superheated to about 850 F. and used in proportions up to 30% by weight of the oil charge is admitted by branched and valved lines from conduit 10 to atomizers 9 and 9a, which may be designed to give a swirling effect to the mingling fluid and of the Venturi type to impart a high velocity to the atomized charge. The atomized charge, now at about 650 F., is distributed at high velocity by branched or sectional manifolds 11 and 11a into the upper portions of vaporizing units 6 to 6c, inclusive, where vaporization of the charge is effected in contact withporous absorbent material which has little or no catalytic activity. The contact mass retains, within its pores, the coke and tarry constituents resulting from the vaporizing operation. When the pores of the contact mass become clogged with these deposits, it is necessary to remove the same. This is preferably accomplished by oxidation, a regenerating medium suchas air being admitted by valve controlled branches from a main conduit 12, which connects with manifolds 13, 13a, 13b and 13e, respectively, of vaporizing units 6 to 6c, inclusive, from which lead series of perforated distributing conduits 14, 14a, 14h, and 14o, respectively. The hydrocarbon vapors or the fumes of regeneration, dependent upon whether the units are on stream on in regeneration, issue from units 6 and 6a in chamber 4 by branches of conduit 15, which may be connected by valve 16 either with vapor line'17 or with conduit .18, which discharges into chamber 4. Similarly, vaporizing units 6b and l6c in chamber 5 discharge either vapors or fumes into branches of conduit 15b, which may be connected by valve 16h either with a vapor line 17b or with a conduit 18h which discharges into chamber 5. Vapors from branched line 17 and 17h may be conducted through a cracking unit 19 of any suitable or desired type, or may by-pass the latter. The vapors, either cracked or uncracked, may be conducted away by line 20 which passes through heat exchanger 7.

It is to be understood that, when the apparatus is in operation, the vaporizing units in one of chambers 4 or 5 will be on stream or in vaporizing phase, while the units in the other chamber will be in regeneration or in the deposit removing phase. Assuming now that the apparatus in chamber 4 is on stream and the apparatus in chamber is in regeneration, atomizer 9 will be in operation while atomizer 9a will be closed, and the regenerating medium from conduit 12 will be shut oi from manifolds 13 and 13a, and will be passing into manifolds 13b and 13e, with the result that air will be distributed through the contact masses in converters 6b and 6c to effect combustion of the coke and tarry deposits therein. Valves 16 and 16h will be set, as indicated, so that the vapors discharging into line 15 at about 850 F. will pass into line 17, while the fumes of regeneration discharging into line 15b at about 1050 F. will be discharged through conduit 185 into chamber 5. Since heat must be withdrawn from chamber 5 where an exothermicl plied when needed and accurate regulation of temperature may be effected. The opposite ends of chambers 4 and 5 are also interconnected by a conduit 24, which includes air circulating means, such as a reversible fan 25, and valved vents 26 and 27 on opposite sides of the fan to relieve excess of flue gases in the closed circuit between the chambers. Thus, when the apparatus in chamber 5 is in regeneration and that in chamber 4 is on stream, the various uids will ltravel in the directions indicated by the arrows.

When the function of the apparatus in the two chambers is reversed, the atomized charge will be directed to vaporizing units 6b and 6c, the regenerating medium to vaporizing chambers 6 and 6a, valves 16 and 1Gb will be turned to interconnect conduits 15 and 18 and conduits 15b and 17h, respectively, and fan25 will be reversed.

Referring now to Fig. 2, for a disclosure of the vaporizing units, such as unit 6, it will be noted that the interior of the unit is divided by vertical partitions '28 and 29, which have aligned perforations to receive and support the distributing conduits 14 for the regenerating medium.

horizontal perforated partition or grid 30 near the bottom of the unit supports the porous absorptive contact mass M. Thel portions of the vertical partitions 28 and 29 below grid 30 have openings 28a and 29a to permit the vapors and fumes issuing from the contact mass through the perforations in the grid to pass into discharge conduit 15. 'I'he branched connections from manifold l1 conduct the atomized charge into a series of distributors 31, 32 and 33 disposed in the sections of unit 6 above contact mass M and provided on their under faces with suitable perforations or nozzles for spraying the atomized charge uniformly into contact mass M. A screen 34 of suitable foraminous material is interposed between distributors 31, 32 and 33 and .the contact mass to break the force of the jets so as to prevent channelling ofthe contact mass and to assist in the distribution of the charge.

Any inert porous material, preferably in suitable form for regeneration in situ, may be utilized for contact mass M, such as molded pieces of china clay, broken fragments of brick, pieces of pumice stone, etc. One form of material which is particularly suitable is the porous carrier disclosed in United States Patent No. 1,318,403, issued August 11, 1931, to Alfred Joseph. Since the coeilicient of heat transfer of such a mass is very poor, it is -a'principal object of the invention to bring the oil to be treated to as high a temperature as possible and to distribute it at once over the contact mass. To 'his end, the charge is heated as high as possible, and then atomized by an inert gaseous material such as steam which is superheated to the .temperature at which the vapors are to leave the apparatus. The atomized charge is then distributed quickly and evenly through the contact mass while it is still in minute dispersion and thoroughly mingled with the vehicle medium, as in the form of a fog. To accomplish this, the atomized charge is directed at high velocity, and the manifolds and connections are designed to maintain, so far as possible, the velocity created at the atomizing nozzle, in order that the charge may reach the contact mass while still in atomized condition.

It is to be understood that the use of the herein disclosed arrangement for exchanging heat between adjacent chambers is not confined to vaporiizng or viscosity breaking operations but s adaptable to any operations which employ contact masses capable of regeneration or purincation by oxidation. However, with masses having catalytic or selective adsorptive properties which are impaired or destroyed by overheating, it may be preferable to cool the fumes of the oxidizing reaction and to recirculate them through the contact mass as `a diluent for the regenerating medium, thereby to effect at least partial control of the regenerating temperature. In such a case, fume connections 18 and 18h (Fig. 1) would be omitted and a suitable circuit for the fumes would bevprovided such as that disclosed in my copending application, Serial No. 604,997, led April 13, 1932.

I claim as my invention:

1. In chemical reactions involving the treatment of hydrocarbons and use of contact masses in converters disposed in adjacent but separate chambers with the converters in the separate chambers alternately in exothermic reaction and in endothermic reaction, the process of eiecting heat exchange which comprises circulating a convective medium between and through the chambers to convey heat from the exterior of a converter in exothermic reaction in one chamber to the exterior of a converter in endothermic reaction in another c ber, and modifying the heat content of said medium as it leaves one chamber and before it enters the other chamber.

2. In chemical reactions involving the treatment of hydrocarbons and use of a contact mass in converters disposed in adjacent but separate chambers with the portions of the mass in the converters in the separate chambers alternately on stream and in regeneration by oxidation, the process of effecting heat exchange which comprises circulating a convective medium between and through the chambers to convey heat from the exterior of a converter in regeneration in one chamber to the exterior of a converter on stream in another chamber, modifying when necessary the heat content oi' said medium after leaving one chamber and before entering another, and reversingthe direction of movement of said medium with each changein the function of the converters. A

3. In chemical reactions involving the' treatment of hydrocarbons `and use of a' contact mass in converters disposed in adjacent chambers with the portions of themass in the chambers alternately on stream and in regeneration by oxidation, the process of eil'ecting heat exchange which comprises' circulating a convective medium between and through the chambers to convey heat from a converter inregeneration in one chamber to the exterior of a' converter on stream in another chamber, adding hot fumes of re- 'r generation to the convective medium from the converter in regeneration, modifying as required the heat content of the mixed convective medium and fumes after leaving one chamber and before entering another, releasing to atmosphere a part of the mixed convective medium and fumes after leaving the last indicated chamber, and reversing the direction of movement of said medium with each change in the function of the converters.

4. Apparatus for effecting chemical reactions through the use of contact masses comprising an enclosure providing adjacent but separate chambers, converters in said chambers each containing a contact mass capable of regeneration in situ, means for operating the converters in said chambers alternately on stream with an endothermic reaction and in regeneration with an exothermic reaction, means connecting spaced partsof said chambers to form a circuit including said chambers and independent of said operating means, and means for circulating a convective medium through said circuit and over the exterior of said converters to pick up heat by indirect heat exchange from the exothermic reaction and similarly to give up heat in that manner to the endothermic reaction.

5. Apparatus for effecting chemical reactions providing separate and distinct chambers, a converter. in each chamber, a contact mass in each converter, means for producing an exothermic reaction in the converter in one chamber, means for producing an endothermic reaction` in the converter in the other chamber, conduits connecting similar parts of said chambers together `to form a circuit which includes said chambers and a reversible impeller associated with one of said conduits to force a heat convective medium through said circuit in either direction over the exterior of said converters to pick up heat by indirect heat exchange from the exothermic reaction and similarly to give up heat in that manner to the endothermic reaction.

6. Apparatus for effecting chemical reactions providing separate and distinct chambers, a converter in each chamber, a contact mass in each converter, means for producing simultaneously an exothermic reaction in the converter in one chamber and an endothermic reaction in the converter-in the other chamber, means for alternating the reactions in said converters, lconduits interconnecting spaced parts of both chambers to form a circuit, means in one of said conduits for sending a. heat convective medium through said circuit in either direction over the exterior of said converters to pick up heat by indirect vheat exchange from the exothermic reaction and similarly to give up heat in that manner to the endothermic reaction, means for modifying the heat content of said circulated medium in the other of said conduits, and means for venting said circuit.

.7. In combination, an enclosure providing adjacent chambers, converters in said chambers having inert absorptive material therein capable of regeneration in situ by oxidation, the converters in said chambers being alternately on stream and in regeneration, means supplying a heavy hydrocarbon in liquid form, means for atomizing said hydrocarbon and distributing it over said absorptive material in said converters, means interconnecting said chambers to-form a circuit, and means for circulating a convective medium through said circuit selectively in either direction to transmit the heat of regeneration of the converters in one chamber tothe exterior of the converters in the other chamber receiving the atomized charge.

8. In combination, an enclosure providing adjacent chambers, converters in said chambers having inert absorptive material therein capable of regeneration in situ by oxidation, the. converters in said chambers being alternately on stream and in regeneration, means supplying a heavy hydrocarbon in liquid form, means for atomizing said hydrocarbon and distributing it over said absorptive material infsaid converters, means interconnecting said chambers to form a circuit, means for circulating aconvective medium through said circuit selectively in either direction to transmit the beat vot regeneration of the converters in one chamber to the exterior of the converters in the other chamber receiving the atomized charge, and means in said circuit intermediate said chambers for modifying the heat content of said convective medium.

9.' In combination, a converter providing a plurality of reaction chambers each adapted to contain a contact mass, a distributor in the upper part of each chamber to be above the contact mass therein, and means for directing an atomized charge of high boiling hydrocarbon liquid at high velocity into said distributors and thence into said chambers, said means including an atomizer, conduits of decreasing size extending from said atomizer and connected in series to form a sectional manifold, and branches connecting said manifold to said distributors.

10. In combination, a converter providing chambers, each containing a contact mass, an atomizing nozzle adapted to impart high velocity to a fluid mixture, means for supplying to said -nozzle for such mixture heavy hydrocarbons in liquid form and an inert gaseous-medium up' to 30% by Weight of such hydrocarbons, and means for directing the resulting atomized mixture into said chambers with suicient velocity to maintain the mixture in atomized form until it reaches the contact mass, said last named means comprising an external header made up of sections decreasing in size from the atomizer nozzle, branches extending from each of said sections, and distributors in each of said chambers to' which said branches are connected.

"11. In combination, adjacent converters, each converter providing a plurality of reaction chambers, each chamber containing a contact mass, a distributor in each chamber in each of said converters above the contact mass therein, a common manifold made up of sections of decreasing size and having branches extending from each of said sections to said distributors, a connection for supplying a preheated heavy hydrocarbon liquid to said manifold, and means utilizing a gaseous medium to atomize said hydrocarbon liquid into a fog and to impart a high velocity to the atomized mixture, said manifold, sections, branches and distributors being so arranged and proportioned as to deliver said mixture while still in its atomized form or fog into the contact masses in said reaction chambers.

l2. In combination, adjacent converters, each converter providing a plurality of reaction chambers, each chamber containing a contact mass, a distributor in each chamber in each of said converters, a common manifold made up of sections of decreasing size and having branches extending from each of said sections to said distributors, a, connection for supplying a preheated heavy hydrocarbon liquid to said manifold, and an injector at said connectionv supplying superheated steam in excess of by weight of said liquid hydrocarbon charge to atomize the latter into a fog and to impart velocity to the atomized mixture, said manifold, sections, and branches being proportioned and designed to maintain the velocity of the atomized mixture, and said distributors discharging the same still in the form of a fog upon the contact masses in said reaction chambers.

, EUGENE J. HOUDRY. 

